Amino salts of dimerized fatty acids used as auxiliaries for lacquers



United States Patent 9 Claims. (Cl. 106-308) 10 ABSTRACT OF THE DISCLOSURE Novel use of amine salts of dimerized fatty acids as agents of multiple effectiveness for influencing the characteristics of pigments in organic media. The universal usefulness of the products is manifested in that they have an extraordinary effect as sedimentation preventing agents, as auxiliary grinding agents as well as serving to prevent the pigments from floating out.

PRIOR ART To prevent the sedimentation of suspensions (e.g. lacquers, dyes and paints) of high specific Weight pigments, such as barite, red lead, iron oxide red, micaceous iron and others, so-called suspension agents are used. The suspension agents are generally surface-active substances which are adsorbed by the pigment particles in a very thin layer on their surface and are capable of keeping the suspended particles more or less afloat. At the least, these suspension agents to a large extent, prevent the formation of hard, non-stirrable sediments. As suspen- F sion agents, metallic salts or the amino salts of fatty-, resinic-, naphthenic acids or other suitable carboxylic acids, salts of surface-active sulfuric acid derivatives, salts of pure sulfonic acids, salts of constant sulfuric acid semi-esters, have previously been used. Also high-molecular, wax-like substances, which for example, were ob- 0 tained by the polymerization of alkylene oxides or by the action of several equivalent alkylene oxides on alcohols, glycols, carboxylic acids, dicarboxylic acids or hydroxy acids or else by partial esterification of dicarboxylic acids with bivalent alcohols have been used. Moreover, long-chain dialkyl esters of sulfosuccinic acid have been suggested to reduce sedimentation, but as yet have not been used in practice. While all of the aforementioned prior art suspension agents prevent sedimentation, in varyr ing degrees, these agents are not considered effective for other purposes, such as grinding, etc.

The dispersion of pigments and fillers in organic media, that is, the desctruction of the agglomerates formed from the primary pigment grain is a necessary step in the prepa- 5 ration of paints. This process of dispersion, as a rule, is accomplished by milling or grinding with mechanical means such as roller mills, ball mills or equivalent machinery. To shorten the grinding time, various products have been added to the pigment pastes. These products, designated as auxiliary grinding agents, are supposed to reduce the interfacial tension between the pigment grain and the organic media and thereby facilitate the dispersion of the pigment. Prior art Workers have sought to use auxiliary grinding agents in a restrictive sense. That is, only to improve grinding, without any negative secondary action. As auxiliary grinding agents soy lecithin, zinc-naphthenate, salts of surface-active sulfuric acid derivatives, alkylene oxide adducts to alcohols, phenols and carboxylic acids, alkyl esters of sulfo succinic acid and nitrogen derivatives of natural fats such as N- coco-[i-amino butyric acid, stearic propylene diamine dioleate were used.

3,386,845 Patented June 4, 1968 "ice The so-called floating out of pigments occurs frequently during the processing of paints which had been prepared with pigment mixtures. Fundamentally, two ways of floating out are differentiated here. These may be defined as floating out in vertical direction and floating out in horizontal direction. The cause of the floating out in vertical direction (flooding), can be found in the different specific Weights of the pigments used and in certain electrostatic conditions. It may be recognizcd, for example, by variations in the colorings between the moist and dry lacquer film as well as due to the de velopment of colored streaks, when the paint is applied with the brush. Aside from that, there exists a floating out in horizontal direction, which effect has been little clarified as to its causes. It manifests itself by the formation of agglomerates of the individual pigments in the paints, and it becomes visible in the dry lacquer film by the appearance of color spots: the so-called mottle effect. In particular in denser lacquer films colored hexagonal honeycombs, designated as Benard cells, occur frequently on the edges. Both of these floating out phenomena are very disturbing lacquer problems and consequently many attempts have been made to prevent them by the concomitant use of various addition products. The oldest medium used to prevent floating out was soy lecithin, which, however, has an insufficient effect. In many cases floating out may be prevented by a thixotropic increase in viscosity, for example, with thickened castor oil. However, thixotropy is undesired for many lacquer dyes. Also, silicone oils and nitrogen derivatives of natural fats, such as stearic propylene diamine dioleate have been used to limit the floating out eflfect.

The behavior of pigments in organic media is determined by many factors, such as specific weight and nature of the pigments, pigment surface condition, size and shape of the pigment grain, nature and viscosity of the bonding agents, solvents and diluents as well as electrostatic charging phenomena. These large number of influences make it clear, that despite many efforts, no one as yet has succeeded in developing a medium which meets all of the functions combined. That is, no one has developed a medium incorporating therein an agent capable of satisfactorily functioning as a suspension agent, auxiliary grinding agent and also in preventing the floating out phenomena.

OBJECTS OF THE INVENTION Accordingly, it is a primary object of this invention to provide universal agents for influencing the various characteristics of pigments in organic media.

Another object of this invention is to provide agents that act as anti-sedimentation agents, grinding agents and prevent the floating out effect of pigments in organic media.

A further object of this invention is to provide agents that are superior to the previously used substances in regard to total characteristics of pigments in organic media.

Another object of this invention is to provide agents that are superior to the previously used substances in regard to sedimentation, grinding and floating out of pigments in organic media.

These and other objects will become apparent as the disclosure continues.

THE INVENTION Accordingly it has now been discovered, that amino salts of dimerized fatty acids are very favorably suitable as universal agents for influencing the characteristics of pigments in organic media, as they are far superior to the previously used substances in regard to the total characteristics required for such agents. It may be, that one or the other of the previously known products in one particular characteristic, as for example, preventing sedimentation in oil-lacquers or facilitating the grinding of certain pigm nts, may prove equivalent to the compounds of this invention, but none of them possess the universal suitability and the marked relationship to the usual lacquers and paints as do the amino salts of deinerized fatty acids.

The preparation of the amino salts of dimerized fatty acids is accomplished according to generally known procedures. For example, the dimerized fatty acid is first heated to about 100 to 120 C. and an amount of amine, equimolar to the acid number of the dimerized fatty acid, is thereafter stirred into the dimerized fatty acid. The reaction mixture is allowed to stand at about 100 to 120 C. for 1 hour and thereafter diluted with suitable solvents.

The dimerized fatty acids, suitable for the preparation of the amino salts of this invention may be obtained according to known mehods by dimerization of monoand multi-unsaturated fatty acids having a carbon chain of from 11 to 22 carbon atoms. The natural fatty acids, which are preferred, usually have 18 carbon atoms.

Suitable fatty acids are for example: undecylemic acid, palmito-oleic acid, oleic acid, elaidic acid, linoleic acid, erucic acid, brassidic acid as well as mixtures of fatty acds. The fatty acids may be obtained from products such as: olive oil, rapeseed oil, palm oil, peanut oil, animal oil, soy oil, cottonseed oil, safflower oil, tall oil, linseed oil and corn oil. Generally, commercial mixtures of dimerized fatty acids, contain from 15 to 25% of trimerics and higher polymers and small amounts of monomerics. Trimerics and high polymers, in amounts up to 25%, do not adversely effect the use of these commercial mixtures for purposes of this invention. However, monomerics in amounts over 3% should be removed. This can be conveniently accomplished due to their volatility.

As amine components the primary, secondary and tertiary aliphatic, cycloaliphatic and aromatic as well as heterocyclic, monoand poly-nuclear amino bases may be utilized. The hydrocarbon radicals may also be substituted by alkyl, aryl and hydroxyl groups. When secondary and tertiary amines are used, the radicals present on the amino nitrogen may be identical or different. Aliphatic amines, containing from 12 to 18 carbon atoms are preferred. Among the suitable amines are those of the formula:

Rl-N s wherein R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 22 carbon atoms, hydroxy-lower alkyl, amino-lower alkyl, alkylamino lower alkyl having from 3 to 25 carbon atoms, phenyl, cyclohexyl, and when taken together with the nitrogen, piperidino, morpholino, pipecolino and piperazino; and R is a member selected from the group consisting of hydrogen, alkyl having from 1 to 22 carbon atoms and hydroxy-lower alkyl; and when R R and R taken together with the nitrogen, pyridine, with the proviso that at least one of R R and R is other than hydrogen.

Suitable amines are, for example: ethylamine, diethylamine, diethylenetriamine, propylenediamine, ethanolamine, triethanolamine, hexylamine, octylamine, isooctylarnine, dodecylamine, octadecylaminc, benzylamine, cyclo-hexylamine, aniline, piperidine, morpholine, pyridine and quinoline. Also amine mixtures, as they may be obtained from the fatty acids of natural fats, for example, the so-called cocoalkyl amine, representing an admixture of amines from coconut fatty acid with chain lengths of C to C are suitable. Other amines derived from fatty acids may also be used. Examples of amines with different hydrocarbon radicals are the dodecyldimethylamine,

octadecyl-diethylamine, cyclohexylmethylamine, dicocoalkyl-ethylamine, dimethyl-cocalkylamine, cocoalkylpropylene-diamine.

The amine salts are used generally in the form of neutral salts, wherein each acid group of the dimeric fatty acid is neutralized by an amine radical. Of particular suitability are the amine salts, derived from primary aliphatic amines with 12 to 18 carbon atoms, and among them in turn those which were derived from the amine mixture designated as cocoalkyl-amine. The neutral cccoalkylamine salts are superior to the other products of this invention not only in regard to their effectiveness, but also in regard to their universal usability. Among the various neutral cocoalkyl-arnine salts those of the dimerized soy oiland cottonseed oil fatty acids exhibit the best effect.

The practical utilization of the agents of this invention in pigment suspensions, in particular lacquers and paints, for the purposes of preventing sedimentation and floating out, is accomplished in the usual ways. The amine salts or the amine salt mixtures may be stirred, unblended or undiluted, into the processed lacquer, either before or after the dilution or the standardization of viscosity. The agents may also be worked in the form of high percent solutions or pastes. The fact that the amine salts or the amine salt mixtures of this invention are easily soluble in a series of slightly volatile organic solvents such as lower alcohols and aromatic hydrocarbons or mixtures thereof, is of definite advantage, as this allows an especially uniform adsorption by the pigment with the least mechanical energy expended. The agents of the present invention may also be processed together with the pigments prior to their introduction into the lacquer. This, too, gives satisfactory results.

To be used as auxiliary grinding agents the amine salts or amine salt mixtures may be stirred unblended or undiluted or else in high percent solution into the pigment pastes to be ground and thereafter the thus prepared pastes can be worked up into the final composition. A further possibility is dry or wet grinding with the pigments in the course of pigment preparation, whereby pro-treated pigments are obtained, which have to be admixed only with the required bonding agent to produce the final composition. This working method designated as coating process has become established already to a considerable extent in the pigment producing industry.

The quantities of the agents necessary to obtain satisfactory results may vary depending upon the nature and composition of the pigment and the characteristics and viscosity of the organic medium. Generally, amounts, in weight percent in the range of 0.05 to 5% and, preferably between 0.5 to 2%, based on the amount of pigment used are satisfactory.

The following are examples of the invention which are not to be construed as limitative in any respect.

Example I Sedimentation preventing agents, listed in Table I in amounts of 1%, by weight, based on pigment, were worked into a low-viscose immersion base having the following composition:

Parts by weight Short-chain alkyd resin oil with 25% oil constituent (Alkydal RD 18 75% solution in xylol 40.0 Modified urea-formaldehyde-resin (Plastopal CB 60% solution in xylol 16.6 Iron oxide red 30.0 Pure talc 2.0 Xylol 27.6 n-Butanol 3.4 Tetralin 10.0 Butylglycol 2.0 Benzylalcohol 0.3 Zinc naphthenute with 12% Zinc (Soligen Zinc 0.1

1 Trademark.

The additions were made, in dissolved form, once to the prepared composition as set forth above and once to the pigment paste prior to roll milling. In both cases the results were the same and hence only one set of data is reported in Table I. The immersion base used had a viscosity of 30 to 35 seconds in the DIN (German Industrial Standardization) 4 beaker at 20 C.

The sediments which formed during the standing of the samples were measured by means of the Wass-muth- Boller method (Fats, Soaps, Paints, 1954, No. 2, pages 81-84) at pre-determined intervals and the results are recorded in Table I.

From the results recorded in Table I it is evident that the agents of the present invention (additives 5 to are superior to the conventional additives in preventing sedimentation.

Example II For the performance of a series of tests a heavily pig mented lacquer was used, into which the sedimentation preventing agents were worked in amounts of 1%, by weight, based on pigment, in the manner as described in Example I, The lacquer used had the following composition and a viscosity of about 75 seconds in a DIN 4 beaker at C.

Parts by weight Longchain alkyl resin oil with 67% linseed oil con- 1 Trademark.

The numerical values were obtained by measuring the deposits according to the Wassmuth-Boller method and are reported in Table II.

TABLE I Load required to obtain the proper dispersion in grams Altcr- 1 day 3 days 6 days 14 days days 60 days 90 days 1 Blank test without addition 10 20 50 100 300 1 2 Triethanolamine salt of acid cetyalcohol sulfate 10 10 20 30 100 180 30 Sodium salt of dioctylsulio succinic acid"... 10 20 30 50 150 200 300 Dioleate of fatty propylene diamine 10 20 30 50 150 200 3 5. Neutral triethanolamine salt of dimerized oleic acid with a 16% trimeric content 10 10 10 20 50 100 3 0 6. Neutral trlethanolamine salt of dimerized acids of linseed oil with a 24% trimeric content 10 10 10 20 50 so 250 7. Neutral triethanolamine salt of dimerized acids of soy oil with a 21% trimeric content 10 10 10 20 70 230 8. Neutral diethylenetriamine salt of dimerized acids of soy oil with a 21% trimeric content 10 10 10 20 30 200 9. Neutral benzylamine salt of dimerized acids of cottonseed oil with a 20% trimeric content 10 10 10 20 50 100 30 10. Neutral diemethylcocoalkylamine salt of dimerized acids of soy oil with a 20% trimeric content 10 10 10 10 10 20 190 11. Neutral cocoalkylamine salt of dimerized acids of soy oil with a 21% trirneric content 10 10 10 10 10 20 0 12. Neutral cocoalkylamine salt of dimerized acids of cottonseed oil with a 20% trimeric content 10 10 19 10 10 20 130 13. Acid cocoalkylamine salt of dimerize fatty acids of soy oil 10 10 10 20 30 200 15. Neutral morpholine salt of dimerized fatt with a 21% trimeric content 10 10 10 20 40 220 1 Oompacted. 2 Cemented.

TABLE II Load required to obtain the proper dispersion in grams after 1 day 3 days 6 days 14 days 30 days 60 days 00 days 180 days 1. Blank test without addition 10 10 30 200 300 2. Triethanolamine salt of acid cetylalcohol sulfate 10 10 10 10 10 20 20 30 3. Sodium salt of dioctylsuliosuccinic acid 10 10 10 30 50 200 300 4. Dioleate of fatty propylene diamine 10 10 2O 50 100 200 300 300 5. Neutral triethanolaminc salt of dimerized oleic acid with 16% trimeric content 10 10 10 20 20 30 40 50 6. Neutral tricthanolamine salt of dimerized acids of linseed oil with a 24%:rimerie content. 10 10 10 10 20 20 30 40 7. Neutral triethanolamine salt of dimerized acids of soy oil with a 21% trimeric contcnt. 10 10 10 10 10 20 20 30 8. Neutral diethylenetriamine salt of dimerized acids of soy oil with a 21% trimeric content. 10 10 10 20 30 40 50 50 9. Neutral benzylamine salt of dimerized acids of cottonseed oil with a 20% trimeric content. 10 10 10 20 30 10 50 50 10. Neutral dirnethylcocoalkylamine salt of dimerized acids of soy oil with a 20% trimerrc content 10 10 10 10 10 20 20 30 11. Neutral cocoalkylamine salt of dimerrzed acids of soy oil with a 21% trimeric content. 10 10 10 10 10 10 20 20 12. Neutral cocoalkylamine salt of dimerized acids of cottonseed oil with a 20% trnneric content 10 10 10 10 10 10 20 20 13. Acid cocoalkylamine salt of dimerized fatty acids of soy oil with a 21% trimeric content 10 10 10 10 20 20 30 40 14. Neutral cyclohexylaanine salt of dimerized fatty acids of cottonseed oil with a 20% trimeric content 10 10 10 10 20 20 30 40 15. Neutral morpholine salt of dirnerized fatty acids of soy oil with a 21% trimeric contcnt- 10 10 10 10 10 20 20 30 1 Compacted. 2 Cemented.

In addition to the sedimentation preventing eifect of additives 5 to 15, as reported in Table II, it was also noted that the paints containing the additives of the present invention exhibited superior corrosion resistance, This was many commercial pigments are already pre-treated by the manufacturer and furthermore related data concerning the type and quantity of preconditioning agents is not available. Thus, pigments with a phthalocyanine basis as particularly true with regard to pro-ducts 4, 8, 9, 10, 11, 5 well as various carbon blacks, all of these being of con- 12 and 14. siderable interest in this connection, have been found un- Example III suitable on the strength of pro-tests, because all of the To study the effect of various agents of the present inifi: sangples z t fi H .g s f g ii 2 t: vention versus prior art products, as auxiliary grinding f 3 g iz 2 M t agents, defined mixtures of selected pigments were mixed i Om g Cup 0 en S con 1 e e 1 Cu O with linseed oil and the additive to be studied. The mix- Dun tures were then ground on a three-roll mill. The time re- Miloriblue (Type RN 2 23 of siegle & qulmd obtam a gram 'finene 5s P less than W Manganese violet, an ammonium manganese phosphate determined. Normally several gnndlng passes are required (Type K 21 268 f giggle & CO) for U115 Purpose, that 13 to Say the entlre mammal L b3 Red azo dye based on Z-chloro-4-aminotoluene-S-sulfonic ground has to pass through the rollers several times. id fi a hthoi i (Sj f t scarlgt 22 M f Hence, the grinding bore and the number of passes served siegle & Co.) as a measure of the effect veness of each additive tested. Organic yanow pigment based on 3 1 The mill settings were maintained constant for all passes 90 and acetic acid m xylidide (Benzydine yeuow GR of and the grain fineness was determmed with the siegle & c grindometer.

In order to do without the use of solvents in pet'- The pigments were stirred 1nto the linseed oil varnish forming the grinding tests, and to effect better reproand the additive to be tested was added, in an amount of ducibility, a commercial linseed oil with an acid number 1%, by weight, based on pigment. of 10.0 was used as the binding agent. The proportions For the first series of tests a paste cons1st1ng of 50 of the individual pigments were varied according to the parts by welght of Milori blue and of 200 parts by weight different oil absorption capacities of each pigment type. of linseed 011 varnish was used. Table III shows the re- The selection of suitable pigments was diflicult as sults obtained:

TABLE III Required Grinding Passes Total grind- Grlnding Agents lug time in Evaluation* 1 2 3 minutes 1. Nonylphenol ethoxylated with 4 mols ethylene oxide 7 Z; 60 K 8 Z; 30 K 8 Z; K. 9 Z; 10 K 31 3 2. Nonylphenol ethoxylated with 8-9 nlols ethylene oxide 6 Z; 5 K 7 Z; 20 K 7 Z; 15 K 6 Z; 10 K 26 2-3 3. Nonylphenol ethoxylated with 9 mols ethylene oxide and 7 Z; 55 K 9 Z; 35 K 7 Z; K 8 Z; 15 K. 31 3-4 propoxylated with 10 mols of propylene oxide.

4. Triethanolamine salt of acid cetylalcoliol sulfate 9 Z K 10 Z' 10K 32 3 5. N-cocoalkyl-fi-amino butyric acid 7 Z' 20. 5 1

6. Tallow propylene diamine diolente 8.5 25 2 7. Neutral cocoalkyl-amine salt of dimerized acids of soy oil with a 5 20 1 21% trimeric content.

8. Neutral cocoalkyl-amine salt of dimerized acids of cottonseed 7 Z; 35 K 7 Z; K 7 Z; 10 K 21 oil with a 20% trimeric content.

9. Acid cocoalkyl-amine of dirncrized acids of soy oil with a 21% 6 Z; 50 K 6 Z; K 6 Z; 25 K.. 8 Z; 10 K 26 2-3 trimerie content.

10. Neutral diinethyl cocoalkyl-amine salt of dimerized acids of 6 Z; 35 K 7 Z; 30 K 8 Z; 10 K 21 1 soy oil with a 21% trimeric content.

11. Neutral benzylamine salt of dimerized acids of cottonseed oil 5 Z; 50 K 6 Z; 35 K 7 Z; 25 K 6 Z; 10 K 24 2 with a 20% trimcric content.

12. Neutral diethyleue triaruine salt of dimerized acids of soy oil 7 Z; 35 K. 6 Z; 30 K 8 Z; 10 K 21 1 with a 21% trimerie content.

13. Neutral triethanol amine salt of dinierized acids of soy oil 7Z; K. 7 Z; 30 K. 8 Z; 10 K 22 1 with a 21% trimeric content.

14. Neutral triethanol amine salt of dimerized acids of linseed oil 6 Z: 40 K 7 Z; 30 K. 9 Z; 10 K 22 1 with a 24% trimeric content.

15. Neutral trietlianol amine salt of dimerized oleic acids with a 7 Z; K 6 Z; 45 K. 6 Z; 25 K 7 Z; 10 K 25 2-3 16% trimeric content.

16. Neutral cyclohexyl amine salt 01 dimerized acids of cottonseed 6 Z; 40 K. 8 Z; 30 K 8 Z; 10 K 22 1 oil with a 20% trimerie content.

1?. Neutral morpholine salt of dimerized acids of soy oil with a 7 Z; 35 K.... 7 Z; 25 K 7 Z; 10 K 21 1 21% trimerio content.

18. Without addition 11 Z; K 9 Z; 40 K 11 Z; 25 K 12 Z; 15 K" 43 4 1=very good. 2=good. 3=moderate. 4=poor. Z= Required grinding time; K=Gra1n size, a.

3,386,845 9 10 For the second series of tests a paste of the following composition was used:

Parts by weight Manganese violet dye 60 Linseed oil varnish 200 The results obtained are given in Table IV.

TABLE IV Required Grinding Passes Total grind- Grinding Agents lng time in Evaluation 1 2 3 4 minutes Nonylphenol ethoxylated with 4 mols ethylene oxide 7 Z; 35 K 13 Z; K 1 Nonylphenol ethoxylated with 8-9 mols ethylene oxide 7 Z; 40 K 11 Z; K... 13 Z; 10 K 31 4 p. Nonylphenol ethoxylated with 9 mols ethylene oxide and 10 Z; 45 K... 9 Z; 25 K 11 Z; 10 K 4 propoxylated with 10 mols of propylene oxide. 4. Triethanolainine salt of acid cetyl alcohol sulfate 10 Z; 45 K 9 Z; 30 K 13 Z, 32 4 5. N-cocoalkyl-fl-amino butyric acid 10 Z; K 11 Z; 25 K... 11 Z, 33 4 6. Tallow propylene diarnine dioleate 10 Z; K 14 Z; 10 K.. 24 2 7, Neutral cccoalkyl-amine salt of dimerized acids of soy oil 9 Z; 25 K 11 Z; 10 K 20 1 with a 21% trimeric content. 8. Neutral cocoalkyl-amine salt of dimerized acid of cottonseed 8 Z; 30 K 11 Z; 10 K 9 1 oil with a 20% trimeric content. 9. Acid cocoalkyl-amine salt of dimerized acids of soy oil with a 8 Z; K 9 Z; 30 K 10 Z; 10 K 27 3 21% trimeric content. 10. Neutral dimethyl cocoalkyl amine salt of dimerized acids of 9 Z; 35 K 12 Z; 10 K 21 1 soy oil with a 21% trimeric content. 11. Neutral benzylainine salt of dimerized acids of cottonseed oil 10 Z; 35 K--. 13 Z; 10 K 23 2 with a 20% trimeric content. 12. Neutral diethylene triamine salt of dimei'ized acids of soy 10 Z; 30 K... 11 Z; 10 K 21 1 oil with a 21% trimeric content. 13. Neutral triethanol amine salt of dimerized acids of soy oil 8 Z; 30 K 12 Z; 10 K 20 1 with a 21% trimeric content. 14. Neutral triethanol amine salt of dimerized acids of linseed 9 Z; 25 K 13 Z; 10 K 22 1-2 oil with a 24% trimeric content. 15. Neutral triethanol amine salt of dimerized oleic acids with a 8 Z; 45 K.--. 8 Z; 30 K 9 Z; 10 K 25 2-3 16% trimeric content. 16. Neutral cyclohexyl amine salt of dimerized acids of cottonseed 9 Z; 25 K 12 Z; 10 K 21 1 oil with a 20% trimeric content. 17. Neutral morpholine salt of diinerized acids of soy oil with a 8 Z; 30 K 14 Z; 10 K 22 1-2 21% trimerie content. 18. Without addition. 8 Z; K 10 Z; 30 K-.- 10 Z; 20 K... 11 Z; 10 K... 39 4 i=very good. 2=good. 3=moderate. 4=p00n Z= Required grinding time; K= Grain size, t.

The composition of the pigment paste for the third series of tests was:

Parts by weight Sico-fast scarlet 22M dye Linseed oil varnish 200 45 The grinding test results are reported in Table V.

TABLE V Required Grinding Passes Total grind- Grinding Agents lng time in Evaluation 1 2 3 4 minutes 1 N onylphenol ethoxylated with 4 mols of ethylene oxide 9 Z; 45 K-.. 28 3 Nonylphenol ethoxyiated with 8-9 mols ethylene oxide 10 Z; 36 4 3. Nonylphenol ethoxylated with 8-9 mols ethylene oxide and 12 Z; 41 4 propoxylated with 10 mols of propylene oxide. 4. Triethanolamine salt of acid cetyl alcohol sulfate 14 Z, 40 4 5. N-cocoalkyl-B-amino butyric acid 10 Z, 33 3-4 6. Tallow propylene diamine dioleate. 9 Z; 40 K 22 1-2 7. Neutral cocoalkyl-amine salt of dimerized acids of soy oil 8 Z; 19 1 with a 21% trimeric content. 8. Neutral cocoalkyl-amine salt of dimerized acids of cottonseed 9 Z; 30 K 11 Z; 10 K 20 1 oil with a 20% trimeric content. I 9. Acid cocoalky -amine salt of dimerized acids of soy oil with a 9 Z; 45 K 10 Z; 30 K 12 Z; 10 K 3i 3 21% trimeric content. 10. Neutral dimethyl cocoalkyl-amine salt of dimerized acids of 8 Z; 30 K 12 Z; 10 K 20 1 soy oil with a 21% trimeric content. 11. Neutral bcnzylamine salt of dimerized acid of cottonseed 8 Z; 40 K 7 Z; 30 K 9 Z; 10 K 24 2 oil with a 20% trimeric content. I 12. Neutral diethylene triamine salt of dimerlzed acids of soy 9 Z; 35 K 5 Z; 20 K. 8 Z; 10 K 22 1-2 oil with a 21% trimeric content. I 13. Neutral triethanol amine salt of dimerized acids of soy oil 7 Z; 35 K 13 Z; 10 K 20 1 with a 21% trimeric content. 14. Neutral triethanol amine salt of dlmerized acids of linseed 8 Z; 35 K 9 Z; 25 K.-. 7 Z; 10 K 23 2 oil with a 24% trimeric content. l 15. Neutral triethanol amine salt of dimerized oleic acids with a 8 Z; 35 K .E8 Z; 25 K 9 Z; 10 K 25 2-3 16% trimeric content. 16. Neutral cyclohexyl amine salt of dimerized acids of cotton- 8 Z; 35 K... 7 Z; 25 K 7 Z; 10 K 22 1-2 seed oil with a 20% trimeric content. 17. Neutral morpholine salt of dimerized acid of soy oil with a 9 Z; 35 K... 12 Z; 10 K 21 1 21% triineric content. 18. Without addition 14 Z; 45 K.. 12 Z; 30 K... 15 Z; 10 K 41 4 "1=very good. 2=good 3=moderate. 4=poor. Z Required grinding time; K=Grain size, [1.

1 1 To conduct the fourth series of tests, a pigment paste of the following composition was used:

Parts by weight Benzydine-yellow GR 50 Linseed oil varnish 100 Table VI shows the grinding values obtained:

12 Into the above composition the following agents were added:

A1: blank test without addition agents A2: neutral cocoalkyl-amine salt of dimerized acids of soy oil With a 21% trimeric content TABLE VI Total Grinding Agents Required Grinding Passes (grinding Evaluation ime m 1 2 3 minutes 1. Nonylphenol ethoxylated with 4 mols of ethylene oxide 9Z; 35 K 10Z; 10 K 19 3 2. Nonylphenol ethoxylated with 8-49 mols of ethylene oxide 13 Z; 30 K 10 Z; 10 K 23 4 3. Nonylphenol ethoxylated with 9 mols of ethylene oxide and 13 Z; 35 K 13 Z; 10 K 26 4 propoxylated with 10 mols of propylene oxide. 4. Triethanolamine salt of acid cetyl alcohol sulfate 12 Z; 40 K 12 Z; 40 K 12 Z; 10 K 24 4 5. N-cocoalkyl-B-amino outyric acid 10 Z; 35 K 10 Z; 10 K 20 3 0. Tallow propylene diamine diolcate 7 Z; 30 K 7 Z; 10 K-.. 14 12 7. Neutral cocoalkyl-amine salt of dimerized acids ofsoy oil with Z; 30 K 5 Z; K 6 Z:; 10 K 11 1 a 21% trimeric content. 8. Neutral cocoalkylamine salt of dimerized acids of cottonseed (i Z; 30 K 6Z; 10 K 12 1 oil with a trimeric content. 9. Acid cocoalkylamine salt ofdimerized acids ofsoyoil with 21% 7 Z; 35 K 11Z; 10 K 18 3 trimeric content. 10. Neutral dimethylcocoalkyl-umine salt of dimerized acids of 5 Z; K 7 Z; 10 K 12 1 soy oil with a 21% content. 11. Neutral benzylaminc salt of dimerlzed acids of cottonseed oil 7 Z; K 8 Z; 10 K 15 2 with a 21% trirnerie content. 12. Neutral benzylamine salt of dimerized acids of cottonseed oil 6 Z; 30 K 6 Z; 10 K l2 1 with a 21% trimeric content. 13. Neutral triethanol amine salt ofdimerized acids oisoyollwith 6 Z; 30 K 5 Z; 10 K 11 1 a 21% trimeric content. 14. Neutral triethanol amine Selt oi'dimerized acids oilinsced oil 7Z; 35 K 6 Z; 10 K 13 l-2 with a 24% trimerie content. 15. Neutral triethanol amine salt of dimerized oloic acids with a 7 Z; 35 K 7 Z; 10 K 14 1-2 16% trim eric content. 16. Neutral cyclohexyl amino salt of dimerlzed acids of cotton 6 Z; 30 K 6 Z; 10 K 12 1 seed oil with a 20% triinerie content. 17. Neutral morpheline salt of dimcrized acids of soy oil with a 7 Z; 35 K 6 Z; 10 K 13 1-2 21% trimerie content. 18. Without addition 13 Z; 35 K 13 Z; 10 K 26 4 *1=Very good. 2=good. 3=moderate. 4=poor. Z=Required grinding time, (min); K=Grain size, ,u.

As Tables III to V1 clearly show, the amine salts of dimerized fatty acids, and in particular, the neutral cocoalkyl amine salts of dimerized soyand cottonseed oil fatty acids exhibit by far the best and the most uniform effect, as compared with known nitrogen derivatives of natural fatty acids which produce only a moderate improvement. The other grinding agents, which were used for comparison purposes, belonging to the group of the alkylene oxide addition products, and amine salts of alkylsulfates showed, in general, only a slight effectiveness.

Besides the dispersion effect noted in Tables III to VI, some of the colors proved to be resistant to the prolonged corrosion test in a salt spray apparatus due to the addition product of the present invention. The more favorable results in regard to corrosion resistance were obtained with products 6, 7, 8, 10, 11, 12 and 16.

Example IV mineral spirits 50.0 Long-chain alkyd resin oil with a 64% content of linseed oil, (Alkydal LM 63 100% 11.5

Maleinate resin (Alresat 313 0 P 50% solution in xylol 5.5 Mineral spirits K30 25.0 Decalin 3.2

Dipentene 3 .2 Anti-skinning agent 0.3 Dry cobalt-lead naphthenate (Soligen Co. Pb 1.3

Titanium dioxide 30.0

Carbon black 400 2.0

1 Trademark.

A3: dioleate of tallow propylene diamine (commercial product Duomeen TDO A4: salt of a varnish-tolerant high-molecular acid with a varnish-tolerant long-chain base (commercial product Antiterra U A5: soy lecithin A6: methylpolysiloxane (commercial product Silicone oil Bayer A 1 Trademark.

The test substances were added in an amount of 1%, by weight, based on pigment, with the exception of the silicone oil which was used in an amount of only 0.02%. Each of the agents were worked into the base composition during the grinding process on the roller mill. The milled products were sprayed onto sheet steel and after being dried were photographed at about fold magnification.

The tests showed very distinctly the differences in the formation of Benard-cells, their frequency being a measure for the extent of the floating effect. The product A2, of the present invention, as well as the methylpolysiloxane (A6) show by far the most favorable effect. However, A2 is superior in regard to color distribution, and beyond this it did not exhibit the deteriorations in adhesive strength during the coating process which always occur when using silicone oils. A slight improvement was obtained with A3, whereas A4 and A5 showed no effect at all.

Example V To demonstrate the flooding effect or what is termed floating out in vertical direction the following varnish system proved suitable, as it exhibited a pronouncedly strong flooding effect:

28 parts by weight phenyl modified colophony (Albertol III L were boiled with 21 parts by weight wood oil and 7 parts by weight linseed oil 1 Trademark.

at a temperature of 180 to 200 C. for 20 minutes. After this mixture had been cooled sutliciently, it was admixed with:

Parts by weight Mineral spirits K 30 41.8 Anti-skinning agent 0.6 Dry cobalt-lead-naphthenate 0.6

For purpose of pigmentation,

Parts by weight Titanium dioxide 27 Iron oxide yellow 2 Iron oxide black 6 were added to 100 parts by weight of the lacquer obtained.

The agents preventing the flooding out, which were to be tested, were worked in during pigment grinding at an amount of 1% based on the pigment, with the exception of the silicone oil employed for comparison, which was used only at an amount of 0.02% based on the pigment. The products obtained were applied onto glass sheets and tested in regard to color differentiations between topand bottom surface of the dry lacquer film. The diiferences in the colors are characteristics for the flooding effect.

The individual comparison products have the designation Bl-B6; they correspond in sequence and nature of the products with those listed in Example IV as A1 to A6.

The amine salt of the dimerized fatty acid B2 of the invention showed almost no difference in color and consequently it possessed by far the most favorable effectiveness as an agent for anti-flooding. A slight improvement was noted in the products B3 and B4, while the products B5 and B6 displayed hardly any difference compared with the blank test B1.

The lacquer samples, prepared with the various test substances, were held for several days in test tubes; thereafter, the separation of the pigment constituents were appraised. Due to the flooding efl ect, the variously colored pigments separated distinctly. This separtion into irregularly colored layers could be evaluated as a measure of the extent of the effect. The designation of the individual test tubes was C1 to C6, corresponding with the sequence and nature of the products listed in Example IV under A1 to A6.

The tests proved distinctly, that the lacquer C2, prepared by using the amino salt of dimerized fatty acid, displayed the least separation and that, in other respects, the product of the invention was highly effective as an agent for preventing flooding. In all other cases an extensive separation of the pigments followed, and hardly a difference was noted in comparison to the blank test C1.

Example VI For comparison the same composition as in Example II was employed using the test substances listed in Table VII. The amounts added were based on the pigment. It could be concluded from the corresponding tests, that only when the amino salts of dimerized fatty acids were used, did the top and bottom surfaces of the color films display no diiferentiation in color tone. In other words, only the products of the present invention were suitable as effective agents for preventing the floating out. In the commercial products, which were employed for comparison, the difference in color, compared with the blank test, was hardly diminished.

TABLE VII Test Additive TABLE VII-Continued Test Additive Etiect B 4.... 1% salt of high-molecular acid with a long-chain base 4 (commercial product B 5..-. 1% soy lecithin (commercial product) 3 B 6-.-. 0.02% methylpolysiloxane (commercial product). 4

B 7-... 1% neutral cocoalkyl-amine salt of dimerized acids of *1 soy 0il+0.02% methylpolysiloxane.

B 8--.. Neutral octyl amine salt of dimeric linseed oil fatty 1 acid with a. 24% trimeric content.

B 9-.-. Neutral dodecylamine salt of dimeric linseed oil fatty 1 acid with a 24% trimeric content.

B 10. Neutral octadecylamine salt of dimeric linseed oil fatty 1 acid with a 24% trimen'c content.

B 11. Neutral tetradecylamine salt of dimeric oleic acid with 1 a 16% trimeric content.

B 12... Neutral octadecylamine salt of dimeric oleic acid with 1 a 16% trimeric content.

B 13--. Neutral cocoalkyl-amine salt of dimerized acids of 1 cottonseed oil with a 20% trimeric content.

B 14. Neutral cocoalkyl-amine salt of dimeric oleic acid with 1 a 16% trimeric content.

*Pitting. 1=floating out hardly noticeable. 4=very pronounced floating out.

While certain specific examples and preferred modes of practice of the invention have been set forth it will be understood that this is solely for the purpose of illustration and that various changes and modifications may be made without departing from the spirit of the disclosure and the scope of the appended claims.

We claim:

1. A pigment suspension consisting essentially of a pigment suspended in an organic solvent and 0.05 to 5% by weight based on the pigment of an amine salt of dimers of unsaturated fatty acids of 11 to 22 carbon atoms, the amine salt being derived from an amine selected from the group consisting of pyridine, quinoline and amine of the formula wherein R and R are selected from the group consisting of hydrogen, alkyl of 1 to 22 carbon atoms, hydroxy lower alkyl, amino lower alkyl, alkyl amino lower alkyl of 3 to 25 carbon atoms, phenyl and cyclo hexyl and when taken together with the nitrogen atom, form a heterocyclic selected from the group consisting of piporidino, morpholino and piperazino and R is selected from the group consisting of hydrogen, alkyl of 1 to 22 carbon atoms and hydroxyl lower alkyl, at least one of said Rs being other than hydrogen.

2. A composition according to claim 1, wherein said salt is neutral.

3. A composition according to claim 2, wherein the amine moiety of said neutral salt is derived from an aliphatic amine having from 12 to 18 carbon atoms.

4. A composition according to claim 3, wherein said aliphatic amine is derived from coconut fatty acid.

5. A composition according to claim 4 wherein the dimerized acid moiety of said neutral salt is derived from a member selecter from the group consisting of soy oil fatty acid and cottonseed oil fatty acid.

6. In a process for preparing pigment suspensions in organic solvents, the improvement which comprises adding to said pigment suspensions in organic solvents from about 0.05 to 5% by weight based on the pigment of an amine salt of dimers of unsaturated fatty acids of 11 to 22 carbon atoms, the amine salt being derived from an amine selected from the group consisting of pyridine, quinoline and amine of the formula wherein R and R are selected from the group consisting of hydrogen, alkyl of l to 22 carbon atoms, hydroxy lower alkyl, amino lower alkyl, alkyl amino lower alkyl of 3 to 25 carbon atoms, phenyl and cyclo hexyl and when taken together with the nitrogen atom, form a heterocyclic selected from the group consisting of piperidino, morpholino and piperazino and R is selected from the group consisting of hydrogen, alkyl of 1 to 22 carbon atoms and hydroxyl lower alkyl, at least one of said Rs being other than hydrogen.

7. The process according to claim 6, wherein said salt is neutral.

8. The process according to claim 6, wherein said amine is derived from coconut fatty acid.

9. The process according to claim 8, wherein the dimerized acid moiety of said neutral salt is derived from References Cited UNITED STATES PATENTS 1/1963 Dreher et al. 106308 11/1966 Barron et a1. 106288 TOBIAS E. LEVOVV, Primary Examiner.

0 JAMES E. POER, Examiner. 

